Vat dyestuffs containing sulfonamide groups



United States Patent Office 3,515,732 Patented June 2, 1970 US. Cl.260-354 4 Claims ABSTRACT OF THE DISCLOSURE Vat dyestuffs are providedwhich contain at least one grouping of the formula SO NHR in which Rrepresents a B-sulfatoalkyl group and especially a lower sulfatoalkylgroup. In addition to the said grouping the dyestuffs may containsubstituents that are customarily present in vat dyestuffs, for example,halogen atoms or alkoxy, acylamino or alkyl groups. A process for thepreparation \of such vat dyestuffs is also provided. The

dyestuffs are suitable for dyeing a wide variety of materials, andespecially, for the dyeing or printing of textile materials of naturalor regenerated cellulose by the methods usual for the dyeing or printingof vat dyestuffs. The dyeings and prints produced possess excellentfastness to light and wet fastness.

This is a continuation of copending application Ser. No. 202,959, filedJune 18, 1962, now abandoned, which is a continuation-in-part ofcopending application Ser. No. 860,628 filed Dec. 21, 1959, nowabandoned.

This invention provides vat dyestuifs which contain at least onegrouping of the formula in which R represents a B-sulfatoalkyl group,especially a lower S-sulfatoalkyl group. The term lower in thisconnection means not more than 6 carbon atoms. R advantageouslyrepresents a radical of the formula The term vat dyestuffs comprisesdyestuffs which are capable of being converted by reduction into asocalled leuco-form or vat, possess a better affinity for natural andregenerated cellulose fibers than in the nonreduced form, and can bereconverted by oxidation into the original chromophoric system. Assuitable vat dyestuffs there may be mentioned more especially those ofthe anthraquinone series, for example, those which contain an unmodified9:10-oxoanthracene ring and also those anthraquinones which containfused-on carbocyclic or heterocyclic rings or consist of a plurality ofanthraquinone units, and also vat dyestuffs of perylene tetra carboxylicacid and naphthalene tetracarboxylic acid, and indigoid vat dyestuffs.In addition to at least one grouping of the Formula 1, the dyestuffs maycontain substituents that are customarily present in vat dyestuffs, forexample, halogen atoms or alkoxy, acylamino or alkyl groups.

The invention also provides a process for the manufacture of the abovenew dyestuffs wherein (a) a vat dyestuif containing at least onesulfonic acid halide group is condensed with an amine of the formulaNHzR, in which R has the meaning given in connection with Formula 1, or(b) a vat dyestulf containing at least one sulfonicacid-fl-hydroxyalkylamide group is treated with a sulfating agent or (c)an aminoanthraquinone is reacted with an acylating agent which containsa B-sulfatoalkyl-sulfonamide group, and especially one of the formula or(d) an anthraquinone compound containing a mobile halogen atom isreacted with an amine containing a [3- sulfatoalkyl-sulfonamide group.

In the process as carried out under (a) there are advantageously used asstarting materials vat dyestufis containing at least one sulfonic acidchloride group. Of special interest are vat dyestuffs containing twosuch groups. As examples of suitable starting materials there may bementioned more especially those of the anthraquinone series: 1 :5-dibenzoylamino-anthraquinone disulfochloride, dibenzanthronedisulfochloride, isodibenzanthrone disulfochloride, and also the sulfochlorides of anthanthrone, dibenzpyrene-quinone, pyranthrone,acedianthrone, flavan throne, indanthrone,N:N-diethyldipyrazole-anthronyl, N:N'-diis0propyl-dipyrazole anthronyl,anthraquinone- 2:l(N)1:2-(N) naphthacridone, 1:1-dianthrimide-carbazole,2-2-diphenyl anthraquinone-1:2(N)-dithiazole,2:2"-diphenyl-anthraquinone-S :7 (N -dithiazole.

In addition to sulfochlorides of the anthraquinone series there may bementioned sulfochlorides of indigoid vat dyestuffs, perylenetetracarboxylic acid diimides; perinone dyestuffs and cobaltphthalocyanine. The aforesaid sulfochlorides can be obtained by treatingthe appropriate vat dyestuft with chlorosulfonic acid, or by reactingthe appropriate sulfonic acids with an acid-halogenating agent, such asphosphorus halides, thionyl chloride or chlorosulfonic acid, knownmethods being used for carrying out the aforesaid reactions. Anothermethod of obtaining the sulfochlorides used as starting materialsconsists in acylating an aminoanthraquinone with benzoic acid-sulfonicacid dichloride, whereby a chlorosulfonylbenZoylamino-anthraquinone isobtained.

The reaction of the aforesaid sulfochlorides with an amine of theformula NH R may be carried out in an inert organic solvent, forexample, nitrobenzene, chlorobenzene or ortho-dichlorobenzene at araised temperature. As, on working up, the sulfochlorides are generallyobtained in the form of aqueous suspensions, it is of advantage to carryout the reaction with the amine of the formula NH R in an aqueousmedium, advantageously in the presence of an acid-binding agent, forexample, sodium acetate, sodium hydroxide or sodium carbonate. The molarproportions of the components are preferably so chosen that for eachsulfochloride group in the vat dyestuff at least one molecularproportion of an amine of the formula NHgR is used.

In the form of the process described under (b) there are advantageouslyused as starting materials anthraquinone vat dyestuffs containing one ortwo sulfonic acid fl-hydroxyethylamide groups, for example, monoordisulfonic acid hydroxyethylamides of 1:5-dibenzoylaminoanthraquinone orof dibenzanthrone or of isodibenzanthrone, and also sulfonic acidhydroxyethylamides of anthrathrone, dibenzpyrenequinone, pyranthrone,acedianthrone, fiavanthrone, indanthrone,N:N'-diethyldipyrazole-athronyl, NzN diisopropyl-dipyrazole anthronyl,anthraquinone-2: l (N)-1' :2 (N) naphthacridone, l1'-dianthrimide-carbazole, or 2':2"-dip'henylanthraquinone- 1:2 (N-dithiazole, 2' 2"-diphenylanthraquinone-5 :7 (N) dithiazole.

In addition to the aforesaid sulfonic acid hydroxyethylamides of theanthraquinone series, there may be mentioned sulfonic acidhydroxyethylamides of indigoid vat dyestuffs, perylene tetracarboxylicacid diimides, perinone dyestuffs or cobalt phthalocyanine. Theaforesaid sulfonic acid hydroxyethylamides can be obtained by reactingthe appropriate sulfonic acid chloride with B-hydroxyethylamine, or byreacting a vat dyestuff containing a mobile halogen atom, for example,an aminoanthraquinone of which the amino group is substituted 'by achlorotriazine radical, with an amine of the formula The sulfating ofthe hydroxyethylsulfonamides is advantageously carried out inconcentrated sulfuric acid in the cold, for example, within the range of50 C., and advantageously With at least.5 parts of sulfuric acid foreach part of dyestuff. The sulfating can also be carried out with oleumor chlorosulfonic acid or an addition compound of chlorosulfonic acidwith a tertiary base or amide, for example, pyridine, triethylamine ordimethylformamide.

In the form of the process described under (c) there are used asstarting materials aminoanthraquinones, for example,l:S-diaminoanthraquinone, l-amino-S-benzoylaminoanthraquinone, 4aminoanthraquinone-Z:l(N)- acridones, 4:4- or 4:5'- or 5:5'-diamino-l:l'-dianthrimidecarbazole or S-aminoanthraquinone-Z:l(N)-:2(N)-naphthcarbazole.

As acylating agents containnig a ,B-sulfatoalkylsulfonamide group theremay be mentioned more especially benzoic acid halides and preferably thecompound of the formula These compounds are advantageously obtained byreacting the appropriate sulfobenzoic acid with chlorosulfonic acid toform the benzoic acid sulfochloride, condensing the latter with,B-sulfatoethylamine or fl-hydroxyethylamine to form benzoicacid-(fl-sulfatoethynor -(fl-hydroxyethyl)-sulfonamide, and reacting thelatter with a sulfating agent. As acylating agents there may bementioned also, for example, compounds of the formula The reaction ofthe aminoanthraquinone with the acylating agent is advantageouslycarried out in an inert organic solvent, for example, nitrobenzene,chlorobenzene or ortho-dichlorobenzene, at a raised temperature or inwater. The molecular proportions of the compouents are advantageously sochosen that for each amino group of the anthraquinone radicalapproximately one carboxylic acid chloride group or one group of theformula of the acrylating agent is present.

In the form of the process described under ((1) there are used asstarting materials, more especially reaction products ofaminoanthraquinones with cyanuric chloride,

4 which products contain at least one exchangeable chlorine atom, forexample, the compound of the formula The condensation product is reactedwith an amine containing a sulfonic acid-fl-sulfatoalkylamide group, forexample, the amine of the formula The dyestuffs so chosen can beisolated from the reaction mixture and, notwithstanding the presence ofthe reactive grouping of the Formula 1, they can be worked up intouseful dry dyestuff preparations. They can be isolated from the reactionmixture by filtration. The filtereddyestuff, if desired. after theaddition of a neutral 'or weakly alkaline extender, may be dried. Dryingis advantageously carried out at not too high a temperature, and ifdesired, under reduced pressure.

The dyestuffs of this invention are suitable for dyeing a wide varietyof materials, but especially for dyeing or printing textile materials ofnatural or regenerated cellu-. lose by the methods usual for dyeing orprinting with vat dyestuffs. The dyeings and prints so produced aredistinguished by their excellent fastness to light and wet fastness. Inview of the fact that, in contradistinction to.

the conventional vat dyestuffs, they can generally not be removed to anysubstantial extent from the fiber by means of hot dimethylformamide, itmust be assumed thatthe dyestuffs are chemically bound on the fiber.

The dyeings produced with the dyestuffs of thisinvention are thereforefast to dry cleaning and fast to migration. Fabrics dyed therewith canbe coated with synthetic resins, for example, polyvinyl chloride,Without the dye-- stuff migrating into the plastic, which is especiallyimportant in the manufacture of artificial leather.

The dyestuffs of this invention can generally be vatted very easily andfrequently even at room temperature. The

water-soluble dyestuffs containing a radical of the For-- mula 1 can bevatted very rapidly, even with mild re-' ducing agents such as glucose.As the reactivity of the.

-OSO H groups in the sulfonic acid alkylamide. radical may vary somewhatfrom dyestuff to dyestuff, it isof advantage to select the dyeingconditions, especially the concentration of alkali and reducing agentand also the duration and temperature of dyeing or steaming, dependingon: the dyestuff used. The optimum conditions can easily be.

determined by preliminary tests.

As compared with conventional vat dyestuffs, the Vat dyes of theinvention have the advantage of a better levelling and through-dyeingpower. Moreover, in machinedyeing, even when foaming occurs, they do notcause faulty dyeings due to the precipitation of reoxidized .dye-

stuff, and the pigmentation necessary in dyeing wound.

bodies, for example, cross-wound spools or tricots on a reeling vat,with conventional vat dyestuffs is dispensed with when the dyestuffs ofthe invention are used. .They can also be used in the form of solutionsin the fastrunning padding method, and there is no need for finely thevat, and especially on regenerated cellulose they produce strong andvery level dyeings which have shades similar to those of thecorresponding. dyeings on cotton.

The following examples illustrate the invention, the parts andpercentages being by weight unless otherwise stated, and therelationship of parts by weight to parts by volume being the same asthat of the kilogram to the liter.

EXAMPLE 1 13.8 parts ofl-aminoanthraquinone-6-(p-hydroxyethyl)-sulfonamide (prepared bycondensing l-nitroanthraquinone-6-sulfochloride with monoethanolamineand reduction with sodium hydrosulfide in an aqueous solution) areheated in 150 parts of nitrobenzene with 4.5 parts of2-phenyl-4:6-dichlorotriazine-(1:3:5 for 5 hours with stirring at 150 to155 C. After cooling, the dyestulf which crystallizes in orange needlesis isolated in the usual manner.

parts of the so-o'btained compound of the formula I ll are slowly addedat 0 to 5 C. to 180 parts of concentrated sulfuric acid and dissolvedtherein. The whole is then poured into about 800 parts of ice water andfiltered. The moist filter cake is suspended in about 1000 parts ofwater and neutralized with sodium hydroxide solution. parts of sodiumchloride are added, the mixture is suction-filtered and the filterresidue is dried in vacuo at to C.

In the form of its free acid and the new dyestufi corresponds to theformula and is completely soluble in water, giving a yellow solution.

A solution of 10 parts of the dyestuff in 1000 parts of water is used toimpregnate a cotton fabric so that its weight shows an increase of andthe fabric is then dried. The fabric is then impregnated with a solutioncon taining per liter 40 cc. of sodium hydroxide solution of 36 B., 30grams of Rongalite and 200 grams of sodium chloride, squeezed to aweight increase of 75 and the dyeing is steamed for 1 to 5 minutes atC., thoroughly rinsed in cold water, treated with a 0.5% solution ofsodium bicarbonate, rinsed with Water, soaped for 20 minutes at the boilwith yellow soap-suds, again rinsed, and finally dried. A yellow dyeingis obtained which has good properties of fastness.

6 EXAMPLE 2 10.6 parts of the sulfochloride of the formula (prepared bycondensing the appropriate amine with ben- 20 zoylchloride-4-sulfochloride in nitrobenzene at 140 C.)

are pasted at C. with 120 parts of nitrobenzene. 1.8 parts ofmonoethanolamine are added, and the mixture is stirred for 4 hours at120 to C., then allowed to cool, and the product is filtered off, washedsuccessively 40 with benzene, alcohol and water, and dried.

10 parts of the resulting condensation product are stirred into parts ofconcentrated sulfuric acid at 0 to 5 C., and dissolved therein. Theworking up is carried out as described in Example 1.

45 The new dyestuif corresponds to the formula 70do-G-sm-rrrr-orn-ornosmm and gives a blue solution in water.

Dyeing Process A 1.5 parts of dyestutf are dissolved in 500 parts ofwater 75 at 60 C. The dissolved dye is vatted in a dyebath containing 20parts of sodium hydroxide solution of 30% are slowly added at to C. to180:parts of sulfuric strength and 12 parts of sodium hydrosulfite in3500 parts acid of 100% strength and dissolved therein.1The dyeof water.At 50 C., 100 parts of well wetted cotton are stufif is isolated asdescribed in Example 1; in the form of introduced into this dyebath, anddyeing is carried out its free acid it corresponds to the formula l I oNH J C-NH l l for 45 minutes at that temperature. After the first anddyes cotton and regenerated cellulose by the followminutes, 60 parts ofsodium chloride are added, and after ing method f t yellow tints thefirst minutes, another 60 parts of sodium chloride r d. c n i n k n 0 thbath, idisc j fieutga liiedi ior tigl ily gosped z rt fhe hoil, ri ed 2ODyemg Process B w r n l t r, n dr' g g g sfi fig ia g ig i Z3 3fgstiesslfioperfies 3 parts of dyestuff are suspended 111 500 parts ofwater is obtained at 60 C. The suspended dyestufi is vatted in a dyebathEXAMPLE 3 containing 20 parts of sodium hydroxide solution of 30% w inExample 2 there is used instead of the strength and 12 parts of sodiumhydrosulfite in 3500 parts fochloride first mentioned the sulfochlorideof the formula of water. 100 parts of well wetted cotton are enteredinto 0 0 this dyebath at 50 C and dyeing carried out for 45 I I minutesat that temperature. After the .first :IOminutes, 60 parts of sodiumchloride are added, and after the first 20 minutes, another 60 parts ofsodium chloridev are add H I M ed. The cotton is then removed from 11115bath, oxidized, 0 NH NH 0 neutralized, thoroughly soaped at the boil,rinsed in warm 1 L water and then in cold water, and dried. CIOZS*O 000-50201 A yellow dyeing having good fastness properties isob and thesame procedure followed, there is obtained the dyestutf of the formulaILA I I 0 T F o NHSOz-C CO COC -SO;-NH i IIn-CHzOSOzNa CH2-GH2OS03N2LWhen used according to Dyeing Process A, this dyestufi EXAMPLE 5 yieldsstrong reddish blue dyeings having good fastness properties. 22.4 partsof the condensation product from 2 molecue 1 EXAMPLE 4 lar proportionsof l-aminoanthraquinone and 1 molecular proportion of cyanuric chloridein 250 parts of nitroparts of dlchlom 2 [(5) benzoylammo anthra benzeneare stirred in the presence of 26 parts of 3-amino-- nl -amino:3:5-triazine are asted at 100 C. t/ #3 20 0 p a rts of n itsobenzeneand 15 parts of NzN-dibenzene'sulfomc l N B hydroxyfithylamlde forethy1ani1ine parts of 3 aminobenzene fi hydroxyethyl hours at 180 to 185C. The whole is allowed to cool, lfo id are then strewn and the mixtureis stirmd 60 filtered, and the filter residue is washed successivelywith for 6 hours at to C The dyestuff crystallizes benlfine, alcohol andn then ri dout in very fine, small needles; it is filtered off, washed10 parts of the resulting condensation p t are i h l h l d h i h at anddried, slowly stirred at 0 to 5 C. into parts of sulfuric acid 10 partsof the so-obtained compound of the formula of 96% strength and dissolvedtherein. Working up is carried out as described in Example 1. The newdyestuif corresponds in the form of its free acid to the formula II N ml ll It dyes cotton and regenerated cellulose by the method B describedin Example 4 yellow tints having excellent properties of fastness.

The corresponding derivative of 2-phenyl-4t6-dichlorotriazine-(1:3:5)dyes cotton and regenerated cellulose greenish yellow tints of similarlygood properties. It can be prepared in the following manner:

A solution of 18.9 parts of 2-phenyl-4z6-dihydroxytriazine-(1:3:5) in175 parts of chlorosulfonic acid is heated for 1 hour at 130 to 135 C.and then for 4 hours at 140 to 145 C., poured over about 1000 parts ofice, filtered, and the precipitate is suspended in 500 parts of icewater, accurately neutralized with sodium hydroxide solution,suction-filtered and dried under reduced pressure.

14.4 parts of the resulting sulfochloride are refluxed for 3 hours with84 parts of phosphorus oxychloride and 45 parts of phosphoruspentachloride, then cautiously poured over about 1500 parts of ice,maintained for 30 minutes at C. with energetic stirring,suction-filtered, and the filter residue is washed neutral with icewater, dried and recrystallized from trichlorethylene; the product meltsat 142 C.

6.5 parts of the resulting sulfochloride of the phenyldichlorotriazineare mixed with 100 parts of nitrobenzene In the form of its free acidthe new dyestuff corresponds to the formula When the condensation isperformed with l-amino-S- benzoylaminoanthraquinone instead of withl-aminoanthraquinone, a dyestutf is obtained which dyes cotton andregenerated cellulose from an alkaline hydrosulfite vat golden orangetints having excellent properties of fastness. When1-amino-4-benzoylaminoanthraquinone is used, red tints are obtained, andwith 1:4-diamino-2- acetylanthraquinone blue tints result, both shadeshaving similarly good properties of fastness.

EXAMPLE 6 19.6 parts of the disulfochloride of the formula (preparedfrom the appropriate diamine by condensation withbenzoylchloride-4-sulfochloride in nitrobenzene) are pasted at 140 C.with 300 parts of nitrobenzene. 10 parts of mono-ethanolamine are thenadded dropwise within 1 hour at 140 to 145 C., and the mixture is heatedfor 5 hours at the same temperature, then allowed to cool, and theproduct is filtered off, washed successively with benzene, alcohol andwater, and dried.

10 parts of the resulting condensation product are stirred at 0 to 5 C.into 180 parts of concentrated sulfuric acid and dissolved therein. Thesolution is cautiously poured into ice water and isolated in the usualmanner.

In the form of its free acid the new dyestuff correand 9.3 parts ofl-aminoanthraquinone, and the mixture sponds to the formula is heatedfor 4 hours at 140 to 145 C. The sulfochloride, which crystallizes inthe form of needles, is filtered off, washed with benzene, and dried invacuo.

13 parts of the resulting dyestufl sulfochloride are pasted at 120 C.with 140 parts of nitrobenzene. At the same temperature 4.6 parts ofmonoethanolamine are slowly added dropwise, and the whole is stirred for2 hours at 120 C. and then for 1 hour at 140 C., and allowed to cool.The dyestuff, which crystallizes in the form of fine small needles, isfiltered off, successively washed with benzene, alcohol and water, anddried.

10 parts of the resulting condensation product are added at 0 to 5 C. to180 parts of sulfuric acid of 96% strength and dissolved therein. Thewhole is poured over ice and then worked up as described in Example 1.

NH-C oQ-sm-nu-orncmosonr It dyes cotton and regenerated cellulose froman alkaline hydrosulfite vat red tints.

EXAMPLE 7 11.4 parts of isodibenzanthrone are added at 20 to 25 C. to210 parts of chlorosulfonic acid, and the whole is stirred for 1 hour atthe same temperature, and then heated at to C. until a test portiondissolves in aqueous pyridine of 10% strength, which is the case afterabout 5 hours. The mixture is then cautiously poured over ice, theprecipitated sulfochloride is suctioned oif and washed with ice water.

The isodibenzanthrone disulfochloride so obtained is suspended in theform of a moist press cake in 700 parts of ice water and at 0 to 5 C.treated with 300 parts of monoethanolamine. The mixture is stirred onfor about 2 hours at to C., then allowed to heat up to room temperature,and stirred for a further 15 hours. Finally, the whole is heated for 1hour at 60 to 65 C., suctionfiltered While still warm, and the filterresidue is washed with Water until it is neutral, and then dried.

7 parts of the resulting condensation product are added at 0 to 5 C. to180 parts of sulfuric acid of 96% strength and dissolved within 4 hours.The sodium is then cautiously poured over about 800 parts of ice, andthe precipitate is suctioned off, pasted with 1000 parts of water at 30to 40 C., and neutralized with sodium hydroxide solution. 50 parts ofsodium chloride are added, the whole is suction-filtered, and the filterresidue is dried in vacuo at 60 to 70 C.

In the form of its free acid the new dyestufi corresponds to the formulaSO2NHCH2CH2OSO H OzNHCH CH2OSO H and is completely soluble in water,giving a blue-violet solution. For dyeing it is used in the followingmanner.

Dyeing Process C 1.5 parts of dyestuif are dissolved in 500 parts ofWater at 60 C. The dissolved dyestuff is vatted in a dyebath containing60 parts of sodium hydroxide solution of 30% strength and 12 parts ofsodium hydrosulfite in 3500 parts of water. 100 parts of well wettedcotton are entered at 60% C. into this dyebath, and dyeing is carriedout for minutes at that temperature with the addition of 60 parts ofsodium chloride. The temperature is then raised to 70 C., and another 60parts of sodium chloride added. After 15 minutes, the dyeing temperatureis raised to 80 C. and maintained at that level for 15 minutes. Thecotton is then removed from the bath, oxidized, neutralized, thoroughlysoaped at the boil, rinsed in Warm water and then in cold water, anddried.

There is obtained a brilliant reddish blue dyeing having good fastnessproperties.

EXAMPLE 8 11.4 parts of dibenzanthrone are added at to C. to 210 partsof chlorosulfonic acid, and the mixture is stirred for 1 hour at thesame temperature and then heated at 60 to 65 C. until a test portion issoluble in aqueous pyridine of 10% strength, which is the case afterabout 8 hours. Working up is carried out as described in Example 7.

The dibenzanthrone disulfo-dichloride so prepared is condensed, asdescribed in the second paragraph of Example 7, with monoethanolarnineand then esterified with concentrated sulfuric acid according to Example7, third paragraph.

12 In the form of its free acid the new dyestuif corresponds to theformula It dissolves completely in water, giving a blue solution,

and produces by the method C describedin Example 7 strong reddish bluedyeings having excellent properties of tastness.

EXAMPLE 9 13.3 parts of 3:4:8:9-dibenzpyrenequinone-(5 :10) are added to250 parts of chlorosulfonic acid, and the whole is heated for 1 hour at60 to 65 C., then for 4 hours at to C. and finally for 9 hours at to 103C. The reaction mixture is then poured over ice, isolated in the usualmanner, condensed with monoethanolamine according to Example 7, secondparagraph, and thenesterified with concentrated sulfuric acid acccordingto Example 7, third paragraph.

The new dyestuff gives a yellow aqueous solutionand j propanol-(Z), theprocedure being otherwise the same, there is obtained the dyestuff ofthe formula When, in Example 7, 13.1 parts of dichloroisodibenzanthroneare used instead of 11.4 parts of isodibenzanthrone, and thesulfochlorination is performed at 8085 0., there is obtained thedyestufi of the formula SOzNHC 111-0 1120 s 031%) According to DyeingProcess C, this dyestufi yields vigorous violet dyeings having goodfastness properties.

EXAMPLE 12' 11.4 parts of isodibenzanthrone are introduced into 210parts of chlorosulfonic acid and stirred for one hour at 20-30 C. Thereaction mixture is then heated to 80 C. and stirred at that temperaturefor 4 hours. After cooling, the mixture is poured very carefully on toice-water while stirring thoroughly. The precipitated sulfochloride israpidly filtered ofi and washed with ice-water. The moist sulfochlorideis then introduced into a mixture of 100 parts of fl-aminoethyl-sulfuricacid semi-ester, 300 parts of water and 22 cc. of sodium hydroxidesolution of 30% strength (pH of the solution 9.5) at 510 C., and thereaction mixture heated in the course of 3 hours to 20 C., the pH of thesolution being kept constant by the dropwise addition of concentratedsodium hydroxidesolution. Stirring is continued overnight at roomtemperature; the reaction mixture is then heated for 2 to 3 hours at4050 C. The product is isolated by filtration and dried in vacuo at 4050C. The new dyestuif in the form of the free acid corresponds to theformula EXAMPLE 13 When the condensation described in Example 8 isperformed with 2-aminobutanol-(l) instead of with monoethanolamine, thedyestuif of the formula is obtained.

Bly the Dyeing Process C (see Example 7), this dyestuif yields vigorousreddish blue shades on cotton. The dyeings have excellent fastnessproperties.

EXAMPLE 14 6.2 parts of the compound of the formula 15 16 are introducedinto 150 parts of chiorosulfonic acid and with some ice-water, andcondensed with monoethanldissolved. The solution is stirred at roomtemperature for amine according to Example 7. The resulting sulfonamideminutes, then carefully poured onto ice, the sulfois esterified withconcentrated sulfuric acid as described chloride which precipitates isfiltered off with suction, and there.

washed with some ice-water. The moist sulfochloride is 5 The resultingnew dyestuff corresponds to the formula then quickly introduced into amixture of 50 parts of fl-aminoethyl-sulfuric acid semiester, 150 partsof water, and 11 parts volume of Sodlum hydroxlde It dissolvescompletely in water to give a blue-green tion (pH 9.4), the pH valuebeing kept constant by the dropwise addition of sodium hydroxidesolution of 30% coloratlonwhen used for Dyemg Process Dflt glvesstrength. The batch is then stirred at room temperature 25 g usblue-green dyeing having good .fastness propfor 15 hours. It is thenheated at -50 C. for 2 hours, erties.

the product isolated by filtration, and dried under vacuum at 40-50 C.The resulting dyestuff corresponds to the formula Dyeing Process DEXAMPLE 16 2.2 parts of dyestuff are suspended in 500 parts of 10.3parts of the dyestuif of the formula water of 60 C. The suspendeddyestuif is vatted in a dyebath containing 20 parts of sodium hydroxidesolution of 30% strength and 12 parts of sodium hydrosulfite in 3500parts of water. 100 parts of well wetted cotton are introduced at 60 C.into this dyebath, and N N dyeing carried out at that temperature for 10minutes y with the addition of 60 parts of sodium chloride. The C0 0temperature is then raised to 70 C., and another 60 parts of sodiumchloride added. After 15 minutes, the temperature is raised to 80 C.,and dyeing continued for 15 minutes at that temperature. The cotton isthen removed from the dyebath, oxidized, neutralized, thoroughly soapedat the boil, washed in warm water, I then in cold water, and dried. 00 Avigorous red dyeing having good fasteners properties is obtained. I I

EXAMPLE 15 13.6 parts of the compound of the formula O s s areintroduced into 220 parts of chlorosulfonic acid and the mixture stirredfor 1 hour at room temperature.

It is stirred while being heated to 40 C., and maintained at thattemperature for 2 hours. After that, it

is stirred at 50-55 C. for 3 hours. After cooling, the,

| mixture is carefully poured onto ice, the sulfochloride 0 whichprecipitates is filtered off, washed with someice are introduced into260 parts of chlorosulfonic acid water, and condensed withmonoethanolamine accordand the resulting solution stirred for 24 hoursat room ing to Example 7. Esterification is performed according.temperature. It is then carefully poured onto ice, the to Example 7 withconcentrated sulfuric acid for 10 sulfochloride which precipitates isfiltered off, washed hours at room temperature.

The new dyestuif so obtained corresponds to the formula and dissolvescompletely in water. In the dyeing Process D of Example 14, it yieldsorange dyeings.

EXAMPLE 17 13.4 parts of the dyestuif of the formula 6 parts of thecompound of the formula r rm-ooOsomm-om-omon II o un-coOsomrncm-omon areintroduced at -l2 C. and into 150 parts of 100% sulfuric acid, and forcomplete dissolution, the mixture is stirred for 4 hours at 0-5 C. Theproduct is worked up as described in Example 10.

The new water-soluble dyestuff corresponds to the formula l oNH-oo@-s02-NH-0Hiomosoma and in Dyeing Process A gives golden orangedyeings having good fastness properties.

The first-mentioned compound can be obtained as follows: 2 4.4 parts ofbenzoic acid-para-sulfochloride in 250 parts of nitrobenzene are stirredand heated to -110 C. for 1 hour together with 20 parts of thionylchloride and 0.5 part of dimethylformamide. From the resulting clearsolution, the excess thionyl chloride is distilled off under reducedpressure. 22.9 parts of 5,5'-diamino-1,1'- dianthrimide-carbazole arethen added, and the whole kept at -125 C. for 21 hours. The product isisolated by filtration.

8.6 parts of the sulfochloride of the formula NH-CO ems-O-ooavn t) whichlikewise yields golden orange dyeings having good fastness properties.

2. The vat dyestuffs of the formula w r ,7 mc usomnomcmosoan EXAMPLE 19wherein the substituent groups occupy the positions of the ring systemwhich are occupied by sulfonic acid 10.1 parts of pyranthrone areintroduced into 175 parts chloride groups when the di-chlorosulfonatingstep is of chlorosulfonic acid and the resulting solution heatedconducted under conditions whereinthe ratioof isodito 80-85 C. for 22hours, then carefully poured onto benzanthrone to chlorosulfonic acid isabout 1:18.4 by ice. The sulfochloride which precipitates is filteredoff, weight. Washed with some ice Water, and condensed with mono- 3. Thevat dyestuffs of the formula o 0 k I 1 O OT(SOQNHCHZCHZOSO3H)Zethanolamine according to Example 7. The resulting sulwherein thesubstituent groups occupy those positions of fonamide is esterified withconcentrated sulfuric acid, as the ring system'which are occupied bysulfonic acid described there. chloride groups when thedi-chlorosulfonating step is The water-soluble dyestufr' so obtainedcorresponds to conducted under conditions wherein the ratiov of ditheformula benzanthrone to chlorosulfonic acid is about 1:18.4 by

0 weight. ll 4. A vat dyestufi of the formula Y SO2NH'CH2CHzOSOaNa)2wherein R is fi-sulfato lower alkyl and K isthe lSOdi-r benzanthronylchromophore, wherein the substituent groups occupy those positions ofthe ring systemiwhich are occupied by sulfonic acid chloride-groups whenthe di-chlorosulfonating step is carried out under conditions whereinthe ratio of isodibenzanflhrone to chlorosulfonic,

acid is about 1:18.4 by weight.

When used for Dyeing Process D it yields golden orange References Cited.d 'n s.

1. Dibenzanthrone vat dyestutf which consists essen- 2,051,045 3/1936Holmes et aL tially of chromophoric dibenzanthrone vat dye group-2,731,47 1 peter et 1 ing and two radicals of the formula 3,066,00511/1962 Wedemeyer et a1. .854-

LORRAINE A. WEI'NB'ERGER, Primary Examiner in which R is ---OSO H,wherein the substituent radicals occupy the positions of thedibenzanthrone ring system WEGNER Asslstant Examiner occupied bysulfonic acid chloride groups when conduct- U S Cl X R ing thedi-chlorosulfonating step under conditions wherein r the ratio ofdibenzanthrone to chlorosulfonic acid is 8-34 260-372, M9, 303, 307.5,281,316,309.2,127.4 about 1: 18.4 by Weight.

